ES2328668T3 - DERIVATIVES OF STABLE COLOR POLYCHYLENIMINE, GLASS FIBER LUBRICANTS CONTAINING SUCH DERIVATIVES AND PROCEDURES FOR OBTAINING THEM. - Google Patents

Abstract

Polymer derivatives based upon polyalkyleneimine backbones having a color stabilizing-effective amount of their reactive amino functionalities substituted by either a carboxylic acid or an amino-protecting group such as urea, are disclosed. Methods for preparing said derivatives are also disclosed. Fiber lubricant compositions comprising said polymer derivatives, and the resistance to yellowing associated with such lubricants are disclosed. Also disclosed are methods for treating fibers using the polymer derivatives.

Description

Stable color polyalkyleneimine derivatives, fiberglass lubricants containing said derivatives and procedures to obtain them.

Background of the invention

Fiber processing, including for example, the manufacture of continuous strands of numerous monofilaments, or individual fibers, normally involves the use of equipment that submit monofilaments, split fibers and / or strands you continue at high speed, where the fiber materials are subject to destructive abrasive forces that may be the result of both mutual abrasion between strands and / or between threads and equipment. Whatever the speed, it is usual provide some lubrication for the fibers. Lubricants of fibers are commonly used during the production of many different materials, including fiberglass and fibers synthetics such as polyesters, polyolefins, polyacrylics, polyamides, etc. Fiber lubricants are typically applied to the fibers as a component of a sizing composition, usually immediately after fiber formation, but before the fibers meet forming a beam, and can also be added to fiber materials to provide lubrication during subsequent operation.

One class of fiber lubricants are polyethyleneimine polyamides. Polyethyleneimine polyamides are commonly used to lubricate fiberglass. Polyethyleneimine polyamides generally provide adequate lubrication, where the filaments that break, i.e. lint formation, are limited during processing and the tensile strength of the fiber is generally increased. However, in some applications of the process where the treated material is exposed to heat, air and combinations thereof, polyethyleneimine polyamides may be discolored, evidenced by a yellowing of the material.

A method to combat the nasty yellowing that takes place during said processing of the fibers such as fiberglass that has been treated with sizing compositions including polyamide lubricants from polyethyleneimine, and / or other compounds associated with the yellowing, is the addition of a bleaching agent fluorescent to the sizing composition before being used. The fluorescent whitening agents can be expensive, and they can be cause of problems, in terms of formulation, stability, solubility, etc.

Fading does not necessarily convert the fiber material in unusable, but for aesthetic reasons, the Discoloration should be avoided. So therefore, there is a need in the technique of a fiberglass lubricant with the properties polyethyleneimine polyamide lubricants, which have a stable color when exposed to heat and / or air.

Brief Summary of the Invention

The present invention relates to a derivative polymeric, according to claim 1, and more particularly to a polyalkyleneimine polyamide derivative, which can be used as a fiber lubricant. Derivatives Polymers according to the present invention are particularly suitable as lubricants for the processing of the fiberglass. Polymeric derivatives according to the present invention, and lubricating and sizing compositions which contain such polymeric derivatives, have excellent color stability (i.e. reduced yellowing), when exposed to heat and / or air during, or subsequently to fiber processing, when compared with lubricants commercially available polyalkyleneimine polyamide fibers available.

One aspect of the present invention includes a polymer derivative comprising a structure of polyalkyleneimine having a number of amino functionalities reactive, having each amino reactive functionality at least a reactive hydrogen atom, where an effective amount color stabilizer, the number of amine functionalities reagents have a substituent compound independently selected from carboxylic acids and protective compounds of substituted amine instead of a reactive hydrogen atom, and in where at least about 20% of the compounds substituents are selected from the group consisting of acids carboxylic. In preferred versions of this and other aspects of the present invention, the structure of the polyalkyleneimine is a polyethyleneimine having a molecular weight from about 1000 to about 1800 and the amine protective compound It comprises urea.

Another aspect of the present invention includes a polymer derivative prepared by a process comprising the reaction of a polyalkyleneimine having a number of reactive amino functionalities, with a carboxylic acid and a amine protective compound, under conditions sufficient to derivatize an effective amount of color stabilizer from amino functionalities reactive with either the carboxylic acid or well the amine protective compound, where at least around 20% of the reactive amino functionalities are derivatized with carboxylic acid.

Still, another aspect of the present invention includes a procedure for the preparation of a derivative polymeric, wherein the procedure comprises: (a) provision of a polyalkyleneimine having a number of amino functionalities reactive per mole; (b) reaction of the polyalkyleneimine with at minus a carboxylic acid and an amine protective compound, in where a total molar amount of at least one acid is used carboxylic and the amine protective compound, which is sufficient to derivatize an effective amount of color stabilizer, from number of reactive amino functionalities per mole of polyalkyleneimine. In some preferred versions of this and others aspects of the present invention, a polyethyleneimine having a molecular weight of about 1200 is reacted with acid acetic, pelargonic acid, and urea, where a molar amount Total acetic acid, pelargonic acid, and urea, is substantially equal to the number of reactive amino functionalities per mole of polyethyleneimine. The present invention also includes polymeric derivatives prepared by procedures according to this aspect of the invention.

Another aspect of the present invention includes fiber lubricating compositions and sizing compositions that comprises one or more polymeric derivatives according to one any of the aspects or versions of this invention.

The present invention also includes a method of lubrication of a fiber material, which comprises the provision of a fiber material and contacting the material of fibers with a polymeric derivative according to any one of aspects or versions of the present invention.

As used herein, the terms "react,""substitute," and "derivatize," and their various verb tenses, all refer synonymously to a chemical reaction between a substituent compounds ( i.e. , a carboxylic acid or a amine protective compound), and an amino reactive functionality of a polyalkyleneimine.

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Detailed description of the invention

Useful polyalkyleneimines according with the present invention, include any polyalkyleneimines that have adequate reactive amino functionalities for the reaction with, for example, a carboxylic acid, such as by For example, the polyalkyleneimines described in U.S. Pat. nº 3,597,265, including mixtures of two or more different polyalkyleneimines. As used herein, the expression "amino reactive functionality" refers to any atom of primary or secondary nitrogen of a polyalkyleneimine. Too, as used herein, the expressions "structure of polyalkyleneimine "and" polyethyleneimine structure ", is refer to the part of the resulting polymer derivative according with the present invention, which is derived from the starting material original polyalkyleneimine or polyethyleneimine, respectively.

The structure of polyalkyleneimine or of polyalkyleneimine (terms that are used synonymously when refer to molecular weight), preferably have a molecular weight from about 300 to about 70,000, and with greater preference from about 400 to about 2500. So therefore, when they refer to the molecular weight of the polyalkyleneimine structure of a polymer derivative according With the present invention, these texts include the atoms of reactive hydrogen removed from the original starting material of polyalkyleneimine after substitution with an acid carboxylic or an amine protective compound. Polyalkyleneimines Particularly preferred are polyethyleneimines. The Preferred polyethyleneimines have a molecular weight from approximately 1000 to approximately 1800, being the most preferred at least in part, the molecular weights of approximately 1200, due to its commercial availability and the price.

Polyalkyleneimines and particularly polyethyleneimines, can be obtained commercially from a wide range of sources, including for example, the firm Aceto Corp. (Nippon Shokubai, Japan) and the BASF firm. However, the synthetic production of said polyalkyleneimines can be carried out by known polymerization methods, such as, for example, acid catalyzed polymerization of applicable monomers, including but not limited to, ethyleneimine (aziridine) and substituted aziridines.

The number of reactive amino functionalities per mole that will have any particular polyalkyleneimine, is a molecular weight function and may also vary slightly in each particular molecular weight. For example a polyethyleneimine with a molecular weight of approximately 1200 will have approximately 28 or 29 total amino functionalities per mole of said polyethyleneimine. However from about 7 to about 9 of the number Total amino functionalities are probably tertiary. So by therefore, the number of reactive amino groups in one mole of a polyethyleneimine with a molecular weight of approximately 1200 can vary from about 20 to 21, and may vary even more. Standard and analytical methods already well known, such as by For example, C13 NMR can help determine the number of reactive amino functionalities per mole of a particular polyalkyleneimine, if this is unknown.

The carboxylic acids according to the present invention, preferably have from about 2 to about 26 carbon atoms, including fatty acids ( ie , from 6 to 22 carbon atoms), preferably from about 2 to about 18 carbon atoms. carbon, and more preferably from about 2 to about 9 carbon atoms. The carboxylic acids useful in accordance with the present invention may be linear or branched, and saturated or unsaturated. However, saturated acids are preferred since unsaturated acids may yellow more likely after oxidation.

In certain preferred versions of this invention, mixtures of two or more carboxylic acids are used. From according to this for example, two or more carboxylic acids that they have from about 2 to about 26 atoms of carbon, or preferably from about 2 to about 18 carbon atoms, and more preferably from about 2 to about 9 carbon atoms, together with an amine protective compound, they can be made react with a polyalkyleneimine.

Mixtures of carboxylic acid include, but without being limited to, the fatty acid mixtures found in nature such as those obtained from oils of palm or coconut, often called technical blends. These mixtures techniques may contain several acids of different length of chain, such as a mixture that has two or more acids of 5 up to 10 carbon atoms in length, or two or more acids that It has chain lengths from 12 to 20 carbon atoms. A particularly preferred mixture of two or more carboxylic acids, It comprises pelargonic acid and acetic acid. Acids employees according to the present invention can be obtained commercially or obtained from natural sources by distillation. Unnatural fatty acids, which have a surplus number of carbon atoms can also be obtained commercially or by known synthetic procedures, such as oxidation of nonyl alcohol in the case of pelargonic acid. He acetic acid, or other short chain acids, can be used together with a long fatty acid, to impart solubility to water to the resulting polymer derivatives.

The useful amine protective compounds according to the present invention are capable of reacting with primary and secondary amine functionalities, with a sufficiently favorable balance (thermodynamic, synthetic, or otherwise), to replace the reactive amino functionalities present in a polyalkyleneimine, which are not otherwise substituted by the carboxylic acid (s), used in accordance with the present invention, so that an effective amount stabilizing the color of the number of reactive amino functionalities in The structure of the polyalkyleneimine is substituted ( that is , they react with or are derivatized by either a carboxylic acid or an amine protective compound). In general, according to the present invention, an "effective amount stabilizing the color"), means an amount that is at least about 60-65% of the total number of reactive amino functionalities present in a given polyalkyleneimine structure. In preferred versions of the present invention, at least about 75% of the number of reactive amino functionalities of the polyalkyleneimine structure is substituted. In more preferred versions of the present invention, at least about 80% and at least about 90% of the number of reactive amino functionalities of the polyalkyleneimine structure is substituted. Even more preferably, an amine protective compound, used in accordance with the present invention, will react with the reactive amino functionalities of the polyalkyleneimine with a sufficient favorable balance, so that at least about 92% of the number of functionalities are substituted reactive amino of the polyalkyleneimine structure, and in the most preferred versions of the present invention, at least 94% of the number of reactive amino functionalities will be substituted.

The amine protective compounds useful according to a preferred version of the invention, they include, but are not limited to, urea and ureas substituted according with the general formula (I), isocyanates, cyanamides and cyanamides substituted, haloformates, azidoformates, sulfonyl halides, carbonates, dicarbonates, and methylating agents.

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one

where each R independently each other, represents a hydrogen atom or an alkyl group or aryl that has up to 30 carbon atoms. Urea compounds useful in accordance with the present invention, include urea unsubstituted (CO (NH2) 2), substituted urea with N, urea substituted with N, N ', urea substituted with N, N, urea substituted with N'N ', and urea substituted with N, N, N', N '. Any substituent that does not interfere with the reaction between the group urea carbonyl and reactive amino functionalities remaining may be present in a polyalkyleneimine, including for example, alkyl substituents having 1 to 30 atoms carbon, which can be linear or branched and cyclic or acyclic

Some compounds within the big classes of compounds mentioned above, may not react with a sufficiently favorable balance to be considered a compound Preferred or even suitable amine protector. For example, him dimethyl carbonate does not provide a polymer derivative that have at least about 90% of its functionalities amino reagents substituted according to the present invention. However, other more reactive amine protective compounds they may be effective but they could be considered too expensive, such as some more reactive carbonates, or too toxic, such as dimethyl sulfate. The Preferred amine protective compounds include, but are not limited to, urea and ureas substituted according to the formula general (I), isocyanates, cyanamides and substituted cyanamides. Most preferred amine protective compounds include, but not are limited to, urea and ureas substituted according to the general formula (I), where each R independently from each other, represents a hydrogen atom, or an aliphatic hydrocarbon group that has up to 9 carbon atoms, and even more preferably that has no more than 3 carbon atoms. The protective compound of most preferred amine is unsubstituted urea ("urea"), in Part due to its low price.

Isocyanates useful as compounds amine protectors, include monofunctional isocyanates, such as, for example, ethyl isocyanate, octyl isocyanate and phenyl isocyanate, to name a few. Cyanamide and substituted cyanamides, including mono and cyanamides disubstituted, where the substituents are selected between the alkyl or aryl groups having up to 30 atoms of carbon, can also be used.

As described above, derivatives Polymers according to the present invention, comprise polyalkyleneimine structures with an effective amount color stabilizer of the number of amino functionalities reagents in the structure substituted by, or an acid carboxylic or an amine protective compound. The methods according to the present invention, which claim the provision of polymer derivatives that satisfy said substituent criteria, will react preferentially with a polyalkyleneimine with one or more carboxylic acids and at least an amine protective compound according to the amounts described below.

The procedures for the preparation of polymeric derivatives according to the present invention, they generally consist of the reaction of a polyalkyleneimine with at least one carboxylic acid and a protective compound of amine, where a total molar amount of at least a carboxylic acid and the amine protective compound which is enough to derivatize an effective stabilizing amount of color of the number of reactive amino functionalities per mole. The total molar amount of at least one carboxylic acid and the amine protective compound, which is sufficient, is generally equivalent to the number of reactive amino functionalities there are What to replace. For example, approximately 22 to 23 moles of Total carboxylic acid and amine protective compound should react with a polyalkyleneimine structure that had 30 reactive amino functionalities per mole, to produce a derivative polymeric that had at least about 75% of the substituted amino reactive functionalities.

The acid (s) carboxylic (s) and compound (s) amino protector (s), is reacted generally with polyalkyleneimine with a molar ratio acid: protective from about 1: 4 to about 4: 1. An acidic molar ratio: protective, more preferred, is about 2: 3 to about 3: 2. It is even used with more preference an acidic molar ratio: protector from about 1: 1 to about 1.2: 1.

When a mixture of acids is used carboxylic, the molar ratio of acids can be adjusted from any necessary way to provide more lubrication or greater water solubility, etc. For example, when used together acetic acid and pelargonic acid, a molar ratio Preferred from pelargonic acid to acetic acid is from approximately 9: 1 to 1: 9, being most preferred, approximately 2: 3.

Polymeric derivatives according to the The present invention can be prepared by reacting a polyalkyleneimine with a carboxylic acid (s), and an amine protective compound (s), either sequentially or simultaneously. The polymer derivatives are preferably prepared by heating a polyalkyleneimine to a temperature from about 30 ° C to about 100 ° C, and more preferably from about 50 to about 60 ° C, and slowly adding the appropriate amounts of one or more carboxylic acids. The mixture of polyalkyleneimine and one or more carboxylic acids is then heated and maintained at a temperature of about 160 ° C to about 220 ° C, of preference from about 180 ° C to about 200 ° C, until substantial quantities of distillate are no longer produced. This reaction is preferably left to continue until it is the most complete possible. The partially amidated polyoxyalkyleneimine resulting is then cooled to a temperature from about 100 ° C to about 140 ° C, preferably less than about 120 ° C and more preferably, at approximately 100 ° C. When a protective compound of amine such as a urea or a cyanamide, the procedure can help preferably by adding water to the partially amidated polyalkyleneimine. An appropriate amount of a Amine protective compound is then added, and the temperature rises, preferably slowly, to approximately 140 ° C, and this temperature is maintained slightly raised until the reaction is essentially complete, by example, in the case of urea, when the production of ammonia, and preferably for several hours. For example, the reaction is preferably left that continues for at least approximately 3 to 4 hours. Water may be added, preferably deionized water, to dilute the resulting polymer derivative. He derivative, or optionally the diluted derivative, is transferred to a suitable container Some degree of dilution is preferred where the net polymer derivative can be difficult to handle, such as It is the case of a vitreous composition.

The lubricating and sizing compositions of fibers, according to the present invention, can be prepared by proper dilution of a polymer derivative according with the present invention with a solvent, preferably the Water. These compositions may also include ingredients. additional options, such as antioxidants. Antioxidants that can be included can be of any variety, such as those described in U.S. Pat. No. 5,646,207, including the sodium hypophosphite which is preferred. You can add a antioxidant, such as sodium hypophosphite to a composition fiber lubricant, according to the present invention, in a amount up to about 20% by weight, based on the solids content, and preferably about 10% in weight.

Fiber lubricants, according to the present invention, provide excellent lubrication at the same time that maintain excellent color stability at high temperatures The tendency of polyethyleneimine polyamides to yellow at high temperatures in the air (approximately 100 ° C or more), is significantly reduced in the compositions lubricants according to the present invention. So therefore, the present invention also provides a lubrication method of fiberglass materials in which yellowing After exposure of the materials to heat, it decreases.

The method of the present invention includes the provision of a fiber material and a lubricating composition of fibers or sizing composition, in accordance with the present invention, and bringing the material into contact with the composition. An excess of lubricant or squeeze composition can be drained, and the material to dry. The material can contact a lubricant or a sizing composition by any method known, including for example, immersion, spraying, the roller, the brush. Drying can be done by placing the Fiberglass material in an oven. The times of heating and temperatures can be adjusted depending on the oven or heat source used.

The present invention will now be illustrated with more detail referring to the following specific examples, not limiting

Example one

Reaction with urea, not according to the invention

Approximately 0.250 moles of Epomin® SP-012, a polyethyleneimine with a molecular weight of approximately 1200 (from Aceto Corp., Lake Success, NY; Nippon Shakabi, Japan), were reacted with approximately 1.08 moles of Emery® 1203 pelargonic acid (from Cognis Corp., Cincinnati OH), and approximately 1.48 moles of acid glacial acetic The mixture was heated to 190 ° C and held for about 2 hours The resulting polyethyleneimine polyamide It was allowed to cool to about 100 ° C.

Approximately 60 g of water were combined deionized and approximately 2.36 moles of urea with the polyamide of cooled polyethyleneimine, and the mixture was slowly heated to 130 ° C and then this temperature was maintained for approximately 3.5 hours The resulting yellow foam was cooled to then at 100 ° C.

Deionized water, heated to approximately 50 ° C and in an amount sufficient to obtain an aqueous solution 50%, combined with the polyethyleneimine polyamide derivative, and stirred until the solution was complete.

A 5% solution (in solids) of the product, and its pH was adjusted to 5-6 using acid glacial acetic A square piece of fiberglass fabric without ready, hot cleaned, immersed in the solution and coat. The excess solution was allowed to drain from the tissue and the tissue was then placed in an oven with air flow at 130 ° C for 1 hour to produce a square of fiberglass cloth with a lubricant according to a version of this invention.

The degree of yellowing of the Square fiberglass fabric treated, both quantitative as subjectively, as follows. The whiteness, or absence of yellowing of the square cloth was measured quantitatively by two standard methods. The first evaluation method used was the standard method according to the ASTM E313-00 "Standard practice for Calculating Yellowness and Whiteness Indices from Instrumentally Measured Color Coordinates "(" Standard practice for index calculation yellowing and whiteness from the color coordinates measured instrumentally "), using a spectrophotometer X-Rite® model 978. The results reported in Table I are identified as "We". The procedures and ASTM E313 standards can be obtained from the American Society for Testing and Materials ("American Trial Society and materials "), (West Conshohocken, PA, www.astm.org), and the complete content of ASTM E313-00, is incorporated to this reference. The second evaluation method used was the standard method according to the CIE publication No. 15.2, using an X-Rite® spectrophotometer Model 978. The results mentioned in Table 1 are identified as "W". CIE procedures and standards Publication No. 15.2, can be obtained from the International Commission on Illumination ("International Commission on lighting "), (Vienna, Austria, www.cie.co.at), and content CIE publication No. 15.2 is hereby incorporated as reference. Finally, the subjective evaluation was carried out by visual inspection route and qualified either as white or as yellow, according to the perceivability of any significant yellowing. An evaluation of "white" indicates that no visible yellowing has been observed significant.

Example 2

A polyethyleneimine polyamide prepared according to example 1 was derivatized with ethyl isocyanate
(~ approximately 2.36 moles) at 100-120 ° C for 1 hour, and the resulting polyethyleneimine polyamide derivative was diluted with deionized water to obtain a 40% solution. A 5% solution (in solids) of the product was prepared, and acidified (pH 5-6) with glacial acetic acid. A square of non-squeezed, hot-cleaned fiberglass cloth, identical to that used in Example 1, was immersed in the solution and subjected to a drying treatment identical to that of Example 1. The whiteness measurements of the Square of fabric treated according to this example, were carried out in accordance with the analytical procedures mentioned above in Example 1. The results are reported below in Table 1.

Example 3

A polyethyleneimine polyamide prepared from according to example 1, it was diluted with approximately 250 grams of deionized water, then treated with acetic acid glacial (~ 2.64 moles) and 23% cyanamide solution (~ 2.64 moles) at 100 ° C. The mixture was heated at reflux for about 4.5 hours, then cooled to temperature ambient, to give a 54% solution of an acetate derivative of polyethyleneimine polyamide guanidinium. A solution was prepared. 5% (in solids) of the product (pH 5-6). A square fiberglass cloth without sizing cleaned in hot, identical to that used in example 1, was submerged in the solution and underwent a drying treatment identical to the example 1. The whiteness measurements of the square of treated fabric according to this example they were made according to the analytical procedures referenced above in example 1. The results are reported in Table 1 below.

Example of control

An identical square of fiberglass cloth unprepared, hot cleaned, not subjected to any treatment  with a lubricant, it was evaluated in terms of whiteness, according with the analytical procedures referenced above in the Example 1. The results are listed later in the table. one.

Comparative example one

A polyethyleneimine polyamide prepared from according to example 1, it was derivatized with dimethyl carbonate (? 3.26 mol), and the mixture was heated at reflux for 1 hour. The volatiles were removed by distillation, and the derivative resulting polyethyleneimine polyamide partial carbamate, diluted with deionized water to obtain a 44% solution. Be prepared a 5% solution (in solids) of the product, and acidified  (pH 5-6) with glacial acetic acid. A square of fiberglass fabric without sizing, hot cleaned, identical to that used in example 1, it was immersed in the solution and subjected to the identical drying treatment of Example 1. The whiteness measurements of the square of fabric treated according to This example was performed according to the procedures Analytics referenced above in Example 1. The results They are listed below in Table 1.

Comparative example 2

A polyethyleneimine polyamide prepared from according to example 1, it was diluted with deionized water until about 50% solids, cooled to 50 ° C, and added acrylonitrile (? 2.40 moles) drop by drop. The mixture remained at ~ 50 ° C for about 3 hours, and then cooled to room temperature. Polyethyleneimine polyamide resulting partially cyanoethylated, diluted with deionized water to obtain a 5% solids solution, which was acidified (pH 5-6) with glacial acetic acid. A square fiberglass fabric without sizing, cleaned in hot, identical to that used in example 1, was submerged in the solution and underwent a drying treatment identical to that of Example 1. The whiteness measurements of the square of treated fabric according to this example they were made according to the analytical procedures referenced above in example 1. The results are reported in Table 1 below.

Comparative example 3

A polyethyleneimine polyamide prepared according to example 1 was diluted with deionized water to about 50% solids, cooled to 41 ° C, and formic acid (\96 mmol) was added followed by paraformaldehyde (sim 1.26 mol) . The mixture was heated at 40-60 ° C for approximately 7 hours, and then cooled to room temperature. The partially N- methylated polyethyleneimine polyamide was diluted with deionized water to obtain a 5% solution (in solids), which was acidified (pH 3-4). A square of hot-pressed, non-pressed fiberglass cloth, identical to that used in example 1, was immersed in the solution and subjected to a drying treatment identical to that of example 1. The whiteness measurements of the fabric square treated according to this example were carried out in accordance with the analytical procedures referenced above in example 1. The results are reported in Table 1 below.

Comparative example 4

A square of fiberglass fabric without squeeze, hot cleaned, identical to the one used in the example 1, was immersed in a 5% solution (in solids) (ph 5-6) of a fiberglass lubricant commercially available polyethyleneimine polyamide (Emery® 6717L), and subjected to the identical drying treatment of Example 1. The measurements of the whiteness of the square of treated fabric according to this example, they were made according to the analytical procedures referenced above in example 1. The results are reported in table 1.

Comparative example 5

An identical square of fiberglass cloth, unprepared, untreated, as used in example 1, dipped in a polyamide fiberglass lubricant of commercially available polyethyleneimine (Alubraspin® 226), and underwent an identical drying treatment as in example 1. The whiteness measurements of the square of fabric treated according With this example, they were performed according to the procedures Qualitative analytics referenced above in Example 1. The results are reported in Table 1 below.

TABLE 1

2

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In table 1, "n.q.e." means no quantitatively evaluated.

\ text {*} not according to the invention.

As evidenced by the results presented higher in table 1, the fiber lubricants they contain polyethyleneimine polyamide derivatives according to the present invention, present a significant and unexpected resistance to yellowing The reduced yellowing after drying when compared to commercially available lubricants which contain polyethyleneimine polyamides is significantly  improved. Qualitatively it has been observed that, small or not significant, visible yellowing takes place in fibers treated with lubricants containing polyamide derivatives of polyethyleneimine according to the present invention.

Claims (19)

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1. A polymer derivative that can be obtained through a procedure comprising (a) provision of a polyalkyleneimine having a number of amino functionalities reactive per mole, (b) polyalkyleneimine reaction, so less with a saturated carboxylic acid and a protective compound of amine, selected from the group consisting of isocyanates, cyanamides, haloformates, azidoformates, sulfonyl halides and agents methylants, where a total molar amount of at least minus a saturated carboxylic acid and the protective compound of amine, which is enough to derivatize an amount of at minus 60% of the total number of reactive amino functionalities per mole, where at least 20% of the amino functionalities reagents are derivatized with carboxylic acid saturated. 2. The polymer derivative according to the claim 1, wherein the polyalkyleneimine structure it comprises a polyethyleneimine having a molecular weight from 400 up to 2500, preferably from 1000 to 1800. 3. The polymer derivative according to the claim 1, wherein the saturated carboxylic acids have from 2 to 18 carbon atoms, preferably from 2 to 9 atoms of carbon. 4. The polymer derivative according to the claim 1, wherein the saturated carboxylic acid comprises two or more carboxylic acids of 2 to 18 carbon atoms. 5. The polymer derivative according to the claim 4, wherein the saturated carboxylic acid comprises a mixture of acetic acid and pelargonic acid. 6. The polymer derivative according to the claim 1, wherein the amine protective compounds are selected from the group consisting of isocyanates and cyanamides 7. The polymer derivative according to the claim 1, wherein at least 75%, preferably by at least 80%, more preferably at least 90%, of number of reactive amino functionalities, has a compound substituted substituent instead of at least one atom of reactive hydrogen 8. A procedure for the preparation of polymeric derivative according to claim 1, which comprises (a) and (b), as defined in claim one. 9. The procedure according to the claim 8, wherein at least one carboxylic acid, and the Amine protective compound are reacted with a molar ratio from 2: 3 to 3: 2. 10. The procedure according to the claim 8, wherein at least one carboxylic acid and the amine protective compound are reacted sequentially with the polyalkyleneimine. 11. The procedure according to the claim 8, wherein the polyalkyleneimine comprises a polyethyleneimine having a molecular weight of 400 to 2500, of preference from 1000 to 1800. 12. The procedure according to the claim 8, wherein at least one carboxylic acid it comprises a carboxylic acid having from 2 to 18 atoms of carbon. 13. The procedure according to the claim 8, wherein at least one carboxylic acid It comprises a mixture of two or more carboxylic acids having 2 to 18 carbon atoms. 14. The procedure according to the claim 8 or 9, wherein at least one carboxylic acid It comprises a mixture of acetic acid and pelargonic acid. 15. The procedure according to the claim 14, wherein the pelargonic acid and acetic acid They are reacted at a molar ratio of approximately 2: 3. 16. The procedure according to the claim 8, wherein at least one protective compound of amine has been selected from the group formed by the isocyanates and cyanamides. 17. The procedure according to the claim 8, wherein a total molar amount of by  at least one carboxylic acid and the amine protective compound, the which is enough to derivatize at least 75% of preference at least 80%, more preferably at least 90% of the number of reactive amino functionalities per mole. 18. The polymer derivative, according to the claim 1, which can be obtained by the method of according to any one of claims 9 to 17. 19. A method of lubricating a material fibers, which comprises the provision of a fiber material and contacting said fiber material with the derivative polymeric of any one of claims 1 or 18.

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